WO2022039576A1 - Procédé de préparation de matériau actif de cathode - Google Patents

Procédé de préparation de matériau actif de cathode Download PDF

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Publication number
WO2022039576A1
WO2022039576A1 PCT/KR2021/011173 KR2021011173W WO2022039576A1 WO 2022039576 A1 WO2022039576 A1 WO 2022039576A1 KR 2021011173 W KR2021011173 W KR 2021011173W WO 2022039576 A1 WO2022039576 A1 WO 2022039576A1
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active material
lithium
positive electrode
metal oxide
transition metal
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PCT/KR2021/011173
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English (en)
Korean (ko)
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정원식
윤여준
이강현
이태영
정용조
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주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202180061012.3A priority Critical patent/CN116194409A/zh
Priority to JP2023503486A priority patent/JP7460257B2/ja
Priority to US18/005,234 priority patent/US20230268489A1/en
Priority to EP21858663.4A priority patent/EP4166507A4/fr
Publication of WO2022039576A1 publication Critical patent/WO2022039576A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method of manufacturing a positive electrode active material.
  • a lithium transition metal composite oxide is used as a cathode active material for a lithium secondary battery, and among them, a lithium cobalt composite metal oxide of LiCoO 2 having a high operating voltage and excellent capacity characteristics is mainly used.
  • LiCoO 2 has very poor thermal properties due to destabilization of the crystal structure due to lithium removal and is expensive, so there is a limit to its mass use as a power source in fields such as electric vehicles.
  • lithium manganese composite metal oxide LiMnO 2 or LiMn 2 O 4 etc.
  • lithium iron phosphate compound LiFePO 4 etc.
  • lithium nickel composite metal oxide LiNiO 2 etc.
  • LiNiO 2 has poor thermal stability compared to LiCoO 2 , and when an internal short circuit occurs in a charged state due to external pressure or the like, the positive active material itself is decomposed to cause rupture and ignition of the battery.
  • a nickel-cobalt-manganese-based lithium composite transition metal oxide in which a part of Ni is substituted with Mn and Co, and a part of Ni is substituted with Mn and Al.
  • a nickel-cobalt-aluminum-based lithium composite transition metal oxide has been developed.
  • lithium by-products such as LiOH, Li 2 CO 3 , and Li 2 O prepared at a high temperature during sintering, which are not reacted during the manufacturing process, are present.
  • This lithium by-product increases the strength of the cake containing the lithium composite transition metal oxide.
  • Li 2 O prepared at a high temperature is exposed to the atmosphere as the temperature is lowered and is changed to Li 2 CO 3 or LiOH.
  • LiOH and Li 2 CO 3 act as an adhesive between lithium composite transition metal oxide particles, so that lithium The strength between the composite transition metal oxide particles is increased. Accordingly, the strength of the cake containing the lithium composite transition metal oxide may increase, and problems may occur in post-processing such as ash grinding and sieving. In addition, as the ash grinding conditions become stronger, the lithium composite transition metal oxide may be broken and the cell performance may be deteriorated.
  • the present invention relates to a lithium transition metal oxide having a lithium borate compound formed on the surface by additionally mixing a boron-containing raw material capable of reacting with residual lithium together with a positive electrode active material precursor and a lithium-containing raw material when preparing a lithium transition metal oxide and then calcining.
  • the present invention is a cake containing a lithium transition metal oxide having a lithium borate compound formed on the surface by mixing a cathode active material precursor, a lithium-containing raw material, and a boron-containing raw material having a composition represented by the following Chemical Formula 1 or Chemical Formula 2, followed by firing A first step of manufacturing a; and
  • a second step of preparing a lithium transition metal oxide from which the lithium borate compound is removed by crushing the cake and then washing with water; provides a method for producing a cathode active material comprising.
  • M 1 is at least one selected from Mn and Al,
  • M 2 is at least one selected from B, Mg, Ca, Ti, V, Cr, Fe, Zn, Ga, Y, Zr, Nb, Mo, Ta and W,
  • a boron-containing raw material capable of reacting with residual lithium is additionally mixed with a cathode active material precursor and a lithium-containing raw material, and then calcined,
  • a cake including the lithium transition metal oxide in which the borate compound is formed it is possible to reduce the strength of the cake and the change in strength with time. Accordingly, it is possible to easily perform the pulverization process of the cake, thereby improving productivity and providing a positive electrode active material having excellent quality.
  • the lithium borate compound can be easily removed through washing with water, the performance of the battery can be improved when the positive active material prepared by the method according to the present invention is applied to a secondary battery.
  • the method for producing a cathode active material according to the present invention includes mixing a cathode active material precursor having a composition represented by the following Chemical Formula 1 or Chemical Formula 2, a lithium-containing raw material and a boron-containing raw material, followed by firing, to form a lithium borate compound on the surface A first step of preparing a cake containing a transition metal oxide; and a second step of producing a lithium transition metal oxide from which the lithium borate compound is removed by grinding the cake and then washing it with water.
  • M 1 is at least one selected from Mn and Al,
  • M 2 is at least one selected from B, Mg, Ca, Ti, V, Cr, Fe, Zn, Ga, Y, Zr, Nb, Mo, Ta and W,
  • the method for manufacturing a positive active material according to the present invention includes a third step of drying the lithium transition metal oxide from which the lithium borate compound is removed; and a fourth step of mixing a raw material containing a coating element with the dried lithium transition metal oxide and heat-treating to form a coating layer.
  • the cathode active material precursor having a composition represented by the following Chemical Formula 1 or the following Chemical Formula 2 a lithium-containing raw material and a boron-containing raw material are mixed and fired, and a lithium transition metal oxide having a lithium borate compound formed on the surface. This is the step of making the cake.
  • M 1 is at least one selected from Mn and Al,
  • M 2 is at least one selected from B, Mg, Ca, Ti, V, Cr, Fe, Zn, Ga, Y, Zr, Nb, Mo, Ta and W,
  • the positive electrode active material precursor and the boron-containing raw material capable of reacting with residual lithium together with the lithium-containing raw material are additionally mixed and calcined,
  • the strength of the cake and the change in strength with time can be reduced. Accordingly, it is possible to easily perform the pulverization process of the cake, thereby improving productivity and providing a positive electrode active material having excellent quality.
  • the conventional cathode active material manufacturing method does not mix boron-containing raw materials in the sintering process, so LiOH, Li 2 CO 3 , which does not react in the sintering process on the surface of the lithium composite transition metal oxide, Li 2 CO 3 , Li manufactured at high temperature during sintering Lithium by-products such as 2 O were present.
  • the cake containing the lithium transition metal oxide having the lithium by-product formed on the surface has a high cake strength, causing problems in post-processing such as the pulverization process and the sieving process performed after the calcination process.
  • a cake including a lithium transition metal oxide having the lithium borate compound formed on the surface of the lithium by-product and the boron-containing raw material reacts through the first step is prepared.
  • the cake including the lithium transition metal oxide in which the lithium borate compound is formed has a low cake strength and a small change in cake strength with time, so that post-processing such as a grinding process and a sieving process is easy.
  • the a denotes an atomic fraction of nickel among metal elements in the precursor, and may be 0.6 ⁇ a ⁇ 1, 0.6 ⁇ a ⁇ 0.98, or 0.7 ⁇ a ⁇ 0.95.
  • the b denotes the atomic fraction of cobalt among the metal elements in the precursor, and may be 0 ⁇ b ⁇ 0.4, 0.01 ⁇ b ⁇ 0.4, or 0.01 ⁇ b ⁇ 0.3.
  • the c denotes the atomic fraction of M 1 element among the metal elements in the precursor, and may be 0 ⁇ c ⁇ 0.4, 0.01 ⁇ c ⁇ 0.4, or 0.01 ⁇ c ⁇ 0.3.
  • the d denotes the atomic fraction of M 2 element among the metal elements in the precursor, and may be 0 ⁇ d ⁇ 0.1 or 0 ⁇ d ⁇ 0.05.
  • the lithium-containing raw material is a lithium-containing carbonate (eg, lithium carbonate (Li 2 CO 3 , etc.), hydrate (eg, lithium hydroxide hydrate (LiOH ⁇ H 2 O, etc.)), hydroxide (eg, lithium hydroxide etc.), nitrates (eg, lithium nitrate (LiNO 3 ), etc.) and chlorides (eg, lithium chloride (LiCl), etc.)
  • the lithium-containing raw material is specifically, lithium hydroxide hydrate, more specifically In this case, it may be LiOH ⁇ H 2 O. In this case, the reactivity between the precursor having a high atomic fraction of nickel among the metal elements in the precursor and the lithium-containing raw material may be improved.
  • the cathode active material precursor and the lithium-containing raw material may be mixed in a molar ratio of 1:0.9 to 1:1.2, preferably 1:0.95 to 1:1.15, more preferably 1:1 to 1:1.1.
  • the lithium-containing raw material is mixed below the above range, there is a fear that the capacity of the produced positive electrode active material is reduced. Separation of positive electrode active material particles (causing positive electrode active material impregnation phenomenon) may occur after degradation and firing.
  • the boron-containing raw material may be at least one selected from lithium borate, boron oxide, boric acid, oxo acid of boron, and oxo acid salt of boron.
  • the boron-containing raw material may be, for example, B 2 O 3 , B(OH) 3 , or the like. In this case, the reactivity may be improved because the melting point of the boron-containing raw material is low.
  • the boron-containing raw material is mixed in an amount of 0.01 parts by weight to 5 parts by weight, preferably 0.01 parts by weight to 2 parts by weight, more preferably 0.1 parts by weight to 2 parts by weight based on 100 parts by weight of the positive electrode active material precursor.
  • the content of the boron-containing raw material is within the above range, a direct effect on the firing process is minimized, which is advantageous in terms of improving the performance of the positive electrode active material.
  • the calcination of the first step may be performed at 600°C to 1000°C.
  • the firing temperature may be preferably 650°C to 950°C, more preferably 700°C to 900°C.
  • the sintering temperature is within the above range, other phases (LiM 2 O 4 , cubic structures such as MO) other than the LiMO 2 phase (M is a transition metal) do not exist on the lithium transition metal oxide to be prepared, so it is structurally stable. , there is an advantageous effect in terms of improving the capacity and lifespan of the battery, preventing an increase in resistance, and the like.
  • the sintering in the first step may be performed in oxygen or atmospheric atmosphere. Specifically, the sintering in the first step may be performed in an oxygen atmosphere having an oxygen concentration of 20% by volume or more, and more specifically, the sintering in the first step may be performed in an oxygen atmosphere having an oxygen concentration of 50% by volume or more.
  • the gas other than oxygen may be an inert gas such as nitrogen, helium argon, or the like.
  • there is no other phase (cubic structure, such as LiM 2 O 4 , MO) other than the LiMO 2 phase (M is a transition metal) on the prepared lithium transition metal oxide it is structurally stable, so the capacity and There are advantageous effects in terms of life improvement, prevention of resistance increase, and the like.
  • the calcination of the first step may be performed for 3 to 30 hours.
  • the calcination may be preferably performed for 5 to 20 hours, more preferably 7 to 15 hours.
  • crystal growth of the lithium transition metal oxide may sufficiently occur without deviation (uniformly) for each firing position, and there is an advantageous effect in terms of increasing productivity.
  • the lithium borate compound is a compound formed by reacting residual lithium such as Li 2 O, LiOH, Li 2 CO 3 and the like with the boron-containing raw material, for example, Li 3 BO 3 , Li 2 B 4 O 7 , LiBO 2 , Li 6 B 4 O 9 , Li 2 B 8 O 13 , Li 3 B 7 O 12 , LiB 3 O 5 , and Li 4 B 2 O 5 .
  • the lithium borate compound may be easily dissolved in a washing solution, particularly, a washing solution containing a solvent such as deionized water or distilled water. Accordingly, it can be easily removed through a water washing process in the second step below.
  • the cake containing the lithium transition metal oxide on which the lithium borate compound is formed on the surface prepared through the first step, that is, the cake immediately after firing, is a type A (s-5) tip to IMADA's ZTA-2500N.
  • the cake strength measured with the attached device may be as small as 600N or less.
  • the cake may have a value according to Equation 1 below 0.7, preferably 0.65 or less, and more preferably 0.55 or less. That is, the change over time in the strength of the cake may be small.
  • the strength of the cake after leaving it for 1 week at 25°C and 20% relative humidity was determined by leaving the cake immediately after baking at 25°C and 20% relative humidity for 1 week, and then adding Type A ( s-5) It is a value measured with a device with a tip attached.
  • the second step is a step of preparing a lithium transition metal oxide from which the lithium borate compound is removed by grinding the cake and then washing with water.
  • the pulverization is a process of making a cake containing lithium transition metal oxide agglomerated by firing in the first step into a powder having a size suitable for use as a positive electrode active material.
  • a cake containing lithium transition metal oxide on which the lithium borate compound is formed on the surface prepared through the first step residual lithium such as Li 2 O, LiOH, Li 2 CO 3 and the like hardly exists, Since the strength of the cake is small, grinding conditions may be mild.
  • the pulverization may be performed under conditions of 10,000 rpm or less, preferably 8,000 rpm or less, using a grinder for the cake.
  • the grinder may be a ZM-200 manufactured by Retsch.
  • the washing is a process of removing the lithium borate compound, which is an impurity present on the surface of the lithium transition metal oxide, with a washing solution.
  • the lithium borate compound can be easily removed by washing with water, so that when the positive active material prepared by the method according to the present invention is applied to a secondary battery, the performance of the battery can be improved.
  • the solvent of the washing solution may be at least one selected from deionized water, distilled water, ethanol, acidic aqueous solution, and basic aqueous solution.
  • the acidic aqueous solution may be a solution in which at least one selected from phosphoric acid, acetic acid, oxalic acid, and boric acid is dissolved in distilled water.
  • the basic aqueous solution may be a solution in which at least one selected from lithium hydroxide and lithium carbonate is dissolved in distilled water.
  • the solvent of the washing solution may be deionized water and/or distilled water. In this case, the lithium borate compound may be easily dissolved in the washing solution.
  • the washing solution is added in an amount of 50 parts by weight to 200 parts by weight, preferably 80 parts by weight to 200 parts by weight, more preferably 80 parts by weight to 150 parts by weight based on 100 parts by weight of the cake. may be performed by When the content of the washing solution is within the above range, the lithium borate compound as an impurity may be sufficiently washed, and productivity may be improved.
  • Water washing in the second step may be performed at 5°C to 40°C, preferably at 20°C to 30°C. And, the water washing in the second step may be performed for 3 minutes to 30 minutes, preferably 3 minutes to 20 minutes, and more preferably 3 minutes to 10 minutes.
  • the temperature and time for the water washing process are within the above ranges, the lithium borate compound present on the surface of the lithium transition metal oxide may be easily removed. Accordingly, a gelation phenomenon may not occur when the positive electrode slurry is prepared, and gas may not be generated when applied to a battery. In addition, lithium present in the oxide does not escape during washing, so the performance of the battery may not be deteriorated.
  • the content of the lithium borate compound may be 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less with respect to the positive electrode active material. That is, through the second step, almost all of the lithium borate compound may be removed from the lithium transition metal oxide on which the lithium borate compound is formed. Accordingly, when the cathode active material prepared by the method according to the present invention is applied to a secondary battery, the performance of the battery may be improved.
  • the method for manufacturing a cathode active material according to the present invention may further include drying the lithium transition metal oxide from which the lithium borate compound has been removed.
  • the drying process is a process for removing moisture from the positive electrode active material containing moisture through a water washing process. After removing moisture using a vacuum pump, under a temperature condition of 30°C to 200°C, specifically, 100°C to 150°C Under temperature conditions, it may be dried for 12 hours or more.
  • the method for manufacturing a cathode active material according to the present invention may further include mixing a dry lithium transition metal oxide with a raw material containing a coating element and heat-treating to form a coating layer. Accordingly, a cathode active material having a coating layer formed on the surface of the lithium transition metal oxide may be manufactured.
  • the metal element included in the raw material containing the coating element may be Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S and Y, etc. .
  • the raw material containing the coating element may be an acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing the metal element.
  • boric acid (B(OH) 3 ) and the like may be used.
  • the raw material containing the coating element may be included in a weight of 200 ppm to 2000 ppm based on the dried lithium transition metal oxide.
  • the content of the raw material containing the coating element is within the above range, the capacity of the battery can be improved, and the resulting coating layer suppresses a direct reaction between the electrolyte and the lithium transition metal oxide, so that the long-term performance characteristics of the battery can be improved.
  • the heat treatment may be performed at a temperature of 200 °C to 400 °C.
  • the coating layer may be formed while maintaining the structural stability of the lithium transition metal oxide.
  • the heat treatment may be performed for 1 hour to 10 hours.
  • the heat treatment time is within the above range, an appropriate coating layer may be formed and production efficiency may be improved.
  • the present invention may provide a positive electrode for a lithium secondary battery including the positive electrode active material prepared by the above-described method.
  • the positive active material may have a composition represented by Formula 3 below.
  • M 1 is at least one selected from Mn and Al,
  • M 2 is at least one selected from B, Mg, Ca, Ti, V, Cr, Fe, Zn, Ga, Y, Zr, Nb, Mo, Ta and W,
  • the positive electrode includes a positive electrode current collector, and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector and including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and for example, stainless steel, aluminum, nickel, titanium, fired carbon, or carbon, nickel, titanium on the surface of aluminum or stainless steel. , silver or the like surface-treated may be used.
  • the positive electrode current collector may typically have a thickness of 3 ⁇ m to 500 ⁇ m, and fine irregularities may be formed on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven body.
  • the positive active material layer may include a conductive material and a binder together with the positive active material.
  • the positive active material may be included in an amount of 80 wt% to 99 wt%, more specifically 85 wt% to 98 wt%, based on the total weight of the cathode active material layer. When included in the above content range, excellent capacity characteristics may be exhibited.
  • the conductive material is used to impart conductivity to the electrode, and in the configured battery, it can be used without any particular limitation as long as it has electronic conductivity without causing chemical change.
  • Specific examples include graphite such as natural graphite and artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers, such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one or a mixture of two or more thereof may be used.
  • the conductive material may be included in an amount of 1% to 30% by weight based on the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between the positive active material particles and the adhesion between the positive active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and any one of them or a mixture of two or more thereof may be used.
  • the binder may be included in an amount of 1% to 30% by weight based on the total weight of the positive electrode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the above positive electrode active material. Specifically, it may be prepared by applying the above-described positive active material and, optionally, a composition for forming a positive electrode active material layer prepared by dissolving or dispersing a binder and a conductive material in a solvent on a positive electrode current collector, followed by drying and rolling. In this case, the types and contents of the positive electrode active material, the binder, and the conductive material are as described above.
  • the solvent may be a solvent generally used in the art, dimethyl sulfoxide (DMSO), isopropyl alcohol (isopropyl alcohol), N-methylpyrrolidone (NMP), acetone (acetone) or water, and the like, and any one of them or a mixture of two or more thereof may be used.
  • the amount of the solvent used is enough to dissolve or disperse the positive electrode active material, the conductive material and the binder in consideration of the application thickness of the slurry and the production yield, and to have a viscosity that can exhibit excellent thickness uniformity when applied for the production of the positive electrode thereafter. Do.
  • the positive electrode may be prepared by casting the composition for forming the positive electrode active material layer on a separate support and then laminating a film obtained by peeling it from the support on the positive electrode current collector.
  • the present invention can manufacture an electrochemical device including the positive electrode.
  • the electrochemical device may specifically be a battery, a capacitor, or the like, and more specifically, may be a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, and a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is the same as described above, so detailed description is omitted, Hereinafter, only the remaining components will be described in detail.
  • the lithium secondary battery may optionally further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel surface. Carbon, nickel, titanium, silver, etc. surface-treated, aluminum-cadmium alloy, etc. may be used.
  • the negative electrode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine irregularities may be formed on the surface of the current collector to strengthen the bonding force of the negative electrode active material.
  • it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metal compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy; metal oxides capable of doping and dedoping lithium, such as SiO ⁇ (0 ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide;
  • a composite including the above-mentioned metallic compound and a carbonaceous material such as a Si-C composite or a Sn-C composite, may be mentioned, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • both low crystalline carbon and high crystalline carbon may be used.
  • low crystalline carbon soft carbon and hard carbon are representative, and as high crystalline carbon, amorphous, plate-like, flaky, spherical or fibrous natural or artificial graphite, Kish graphite (Kish) graphite), pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, liquid crystal pitches (Mesophase pitches), and petroleum and coal tar pitch (petroleum or coal tar pitch) High-temperature calcined carbon such as derived cokes) is a representative example.
  • the anode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the anode active material layer.
  • the binder is a component that assists in bonding between the conductive material, the active material, and the current collector, and may be typically added in an amount of 0.1 wt% to 10 wt% based on the total weight of the anode active material layer.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro and roethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, nitrile-butadiene rubber, fluororubber, and various copolymers thereof.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • EPDM ethylene-propylene-
  • the conductive material is a component for further improving the conductivity of the anode active material, and may be added in an amount of 10 wt% or less, preferably 5 wt% or less, based on the total weight of the anode active material layer.
  • a conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • graphite such as natural graphite or artificial graphite
  • carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
  • conductive fibers such as carbon fibers and metal fibers
  • metal powders such as carbon fluoride, aluminum, and nickel powder
  • conductive whiskers such as zinc oxide and potassium titanate
  • conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives may be used.
  • the anode active material layer is prepared by applying and drying a negative electrode mixture prepared by dissolving or dispersing a negative electrode active material, and optionally a binder and a conductive material in a solvent, on the negative electrode current collector, or casting the negative electrode mixture on a separate support. Then, it can be prepared by laminating the film obtained by peeling from this support on the negative electrode current collector.
  • the separator separates the negative electrode and the positive electrode and provides a passage for lithium ions to move, and as long as it is used as a separator in a lithium secondary battery, it can be used without any particular limitation, especially for the movement of ions in the electrolyte It is preferable to have a low resistance to respect and an excellent electrolyte moisture content.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these
  • a laminate structure of two or more layers of may be used.
  • a conventional porous nonwoven fabric for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc. may be used.
  • a coated separator including a ceramic component or a polymer material may be used, and may optionally be used in a single-layer or multi-layer structure.
  • examples of the electrolyte used in the present invention include organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in the manufacture of lithium secondary batteries, and are limited to these. it is not going to be
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without any particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone
  • ether solvents such as dibutyl ether or tetrahydrofuran
  • ketone solvents such as cyclohexanone
  • aromatic hydrocarbon-based solvents such as benzene and fluorobenzene
  • alcohol solvents such as ethyl alcohol and isopropyl alcohol
  • nitriles such as R-CN (R is a linear, branched, or cyclic hydrocarbon group having 2
  • a carbonate-based solvent is preferable, and a cyclic carbonate (eg, ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant capable of increasing the charge/discharge performance of the battery, and a low-viscosity linear carbonate-based compound (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
  • a cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB(C 2 O 4 ) 2 , etc. may be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is included in the above range, the electrolyte may exhibit excellent electrolyte performance because it has appropriate conductivity and viscosity, and lithium ions may move effectively.
  • haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri Ethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
  • One or more additives such as taxdine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be further included. In this case, the additive may be included in an amount of 0.1 wt% to 5 wt% based on the total weight of the electrolyte.
  • the lithium secondary battery including the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics and lifespan characteristics, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful in the field of electric vehicles such as hybrid electric vehicle and HEV).
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
  • the battery module or battery pack is a power tool (Power Tool); electric vehicles, including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Alternatively, it may be used as a power source for any one or more medium-to-large devices in a system for power storage.
  • Power Tool Power Tool
  • electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs);
  • PHEVs plug-in hybrid electric vehicles
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape, a prismatic shape, a pouch type, or a coin type using a can.
  • the lithium secondary battery according to the present invention can be used not only in a battery cell used as a power source for a small device, but can also be preferably used as a unit cell in a medium or large battery module including a plurality of battery cells.
  • a cathode active material precursor having a composition represented by Ni 0.88 Co 0.05 Mn 0.07 (OH) 2 was prepared.
  • LiOH ⁇ H 2 O As a lithium-containing raw material, LiOH ⁇ H 2 O was prepared in an amount such that a molar ratio of the positive electrode active material precursor and LiOH ⁇ H 2 O was 1:1.05.
  • B(OH) 3 was prepared in an amount so as to be 1,000 ppm with respect to the positive electrode active material precursor.
  • the lithium borate compound is formed on the surface of LiNi 0.88 by calcination at 780° C. in an oxygen atmosphere having an oxygen concentration of 90% by volume for 13 hours.
  • a lithium transition metal oxide cake having a composition of Co 0.05 Mn 0.07 O 2 was prepared.
  • the lithium borate compound was LiBO 2 , Li 3 BO 3 , and Li 2 B 4 O 7 .
  • the cake was pulverized at 8,000 rpm using a grinder (ZM-200, Retsch) and mixed with deionized water in a weight ratio of 1:1, washed with water at 25° C. for 5 minutes to remove the lithium borate compound. , using a vacuum pump, filtered for 3 minutes, and dried in a vacuum oven at 130° C. for 12 hours or more, to prepare a lithium transition metal oxide having a composition of LiNi 0.88 Co 0.05 Mn 0.07 O 2 .
  • the lithium transition metal oxide and B(OH) 3 as a raw material containing a coating element an amount to be 1,000 ppm with respect to the lithium transition metal oxide
  • heat treatment at 300° C. for 5 hours in an oxygen atmosphere the A positive active material in which a coating layer containing boron was formed on the surface of the lithium transition metal oxide was prepared.
  • a positive active material was prepared in the same manner as in Example 1, except that B(OH) 3 as a boron-containing raw material was prepared and used in an amount to be 5,000 ppm with respect to the positive electrode active material precursor.
  • a positive active material was prepared in the same manner as in Example 1, except that B(OH) 3 as a boron-containing raw material was prepared and used in an amount to be 20,000 ppm with respect to the positive electrode active material precursor.
  • the lithium transition metal oxide cake having a composition of LiNi 0.88 Co 0.05 Mn 0.07 O 2 was calcined at 780° C. for 13 hours in an oxygen atmosphere with an oxygen concentration of 90% by volume. prepared. Residual lithium such as the unreacted LiOH ⁇ H 2 O and lithium byproducts were present in the lithium transition metal oxide cake.
  • the cake was pulverized at 8,000 rpm using a grinder (ZM-200, Retsch Co.) and mixed with deionized water in a weight ratio of 1:1, washed with water at 25° C. for 5 minutes to remove the residual lithium, It was filtered for 3 minutes using a vacuum pump, and dried in a vacuum oven at 130° C. for more than 12 hours, to prepare a lithium transition metal oxide having a composition of LiNi 0.88 Co 0.05 Mn 0.07 O 2 .
  • lithium transition metal oxide cakes of Examples 1 to 3 which were minimized, have weak strength and a small increase in strength with time change.
  • the lithium transition metal oxide cake of Comparative Example 1 has a large cake strength due to the presence of residual lithium, and the increase in cake strength according to the change over time is also large.
  • Lithium secondary batteries were manufactured using the positive electrode active materials prepared in Examples 1 to 3 and Comparative Example 1, and initial charging capacity and capacity retention rate were evaluated for each lithium secondary battery.
  • each of the positive active materials prepared in Examples 1 to 3 and Comparative Example 1, a carbon black conductive material, and a PVdF binder were mixed in an NMP solvent in a weight ratio of 97.5:1.0:1.5 to prepare a positive electrode slurry.
  • the positive electrode slurry was applied to one surface of an aluminum current collector, dried at 130° C., and rolled to prepare a positive electrode. Meanwhile, a Li metal disk was used as an anode active material.
  • An electrode assembly was prepared by interposing a separator between the positive electrode and the negative electrode prepared above, and then placed inside the battery case, and then the electrolyte was injected into the case to prepare a lithium secondary battery. At this time, an electrolyte solution in which 1M LiPF 6 was dissolved in an EC/EMC/DEC (3/3/4, vol%) organic solvent was injected as an electrolyte to prepare a lithium secondary battery.
  • the lithium secondary battery prepared as described above was charged with a constant current at 25° C. with a current of 0.1C until the voltage reached 4.25V, and then discharged at a constant current of 0.1C until the voltage reached 3.0V.
  • the initial charge capacity values are shown in Table 3.
  • the capacity of the lithium secondary battery was measured by repeating charging and discharging cycles 30 times at a constant current of 0.33C at 45°C in the range of 3.0 to 4.25V.
  • the ratio of the 30th cycle capacity to the 1st cycle capacity was used as the capacity retention rate Thus, it is shown in Table 2 below.
  • Example 1 228.4 97.9
  • Example 2 228.7 97.8
  • Example 3 230.3 97.8 Comparative Example 1 230.3 95.7
  • the initial charging capacity is at the same level, and the capacity It can be seen that the retention rate is excellent. This is because, as described above, the lithium transition metal oxide cakes of Examples 1 to 3 have weak strength, so pulverization occurs well, and cracking of the lithium transition metal oxide that may occur when the strength of the cake is strong during the pulverization process does not occur. am.
  • a lithium transition metal oxide when preparing a lithium transition metal oxide, a cathode active material precursor, a boron-containing raw material capable of reacting with residual lithium together with a lithium-containing raw material is additionally mixed and fired, and a lithium borate compound is formed on the surface of the lithium transition
  • a cake comprising a metal oxide
  • the strength of the cake and the change in strength with time can be reduced.
  • the pulverization process can be easily performed, thereby improving productivity and providing a positive electrode active material with excellent quality.
  • the positive active material prepared by the method according to the present invention is applied to a secondary battery, the effect of improving battery performance can be obtained.

Abstract

La présente invention concerne un procédé de préparation de matériau actif de cathode permettant de réduire la résistance d'un gâteau de matériau actif de cathode et un changement de résistance dans le temps, et, un procédé de préparation de matériau actif de cathode comprenant : une première étape de mélange d'un précurseur de matériau actif de cathode ayant une composition déterminée, d'un matériau contenant du lithium et d'un matériau contenant du bore, et ensuite de cuisson de celui-ci, préparant ainsi un gâteau comprenant un oxyde de métal de transition au lithium ayant un composé de borate de lithium formé sur sa surface ; et une seconde étape de broyage du gâteau, et ensuite de lavage de celui-ci, préparant ainsi un oxyde de métal de transition au lithium duquel le composé de borate de lithium est éliminé.
PCT/KR2021/011173 2020-08-21 2021-08-23 Procédé de préparation de matériau actif de cathode WO2022039576A1 (fr)

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US18/005,234 US20230268489A1 (en) 2020-08-21 2021-08-23 Method of Preparing Positive Electrode Active Material
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JP7460257B2 (ja) 2024-04-02
US20230268489A1 (en) 2023-08-24
JP2023534982A (ja) 2023-08-15
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